Structures of Metal–Organic Frameworks with Rod Secondary Building Units

Schoedel, Alexander; Li, Mian; Li, Dan; O’Keeffe, Michael; Yaghi, Omar M.

doi:10.1021/acs.chemrev.6b00346

Cited by 755 publications

(477 citation statements)

References 281 publications

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“…However, robust and highly porous MOFs based on these ligands are scarce in the literature. [56], [65][66][67] (e.g alcohols) or non-polar (e.g alkyl chains) side chain, which is important for the formation of protein structures. Their rich coordination chemistry (through the carboxylate, amino groups and side chains) makes them as an attractive class of organic ligands for the formation of extended MOF structures.…”

Section: Ligand Design In Mofsmentioning

confidence: 99%

Biologically derived metal organic frameworks

Anderson

Stylianou

2017

Coordination Chemistry Reviews

123

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Metal organic frameworks (MOFs) are extended structures composed of a network of organic ligands and metal ions or clusters connected to each other via coordination bonds. The numerous choices of organic ligands and metal coordination geometries have led to the construction of porous MOFs with various compositions, network topologies, pore sizes and shapes and they possess high surface areas and low densities. The structures of MOFs can be tailor-tuned in such a way that any desired ligand or/and metal ion can be incorporated; this has given to researchers the advantage of designing MOFs for a targeted application. Within this review, we overview recent examples of a sub-class of MOFs namely biologically derived MOFs (bio-MOFs), made of multifunctional and commercially available biologically derived ligands (bio-ligands) such as: amino acids, peptides, nucleobases and saccharides and focus on their coordination chemistry with a variety of metals. Central to this review are four tables detailing the coordination modes of bio-ligands to metals, along with a visual representation of the bio-MOF that is subsequently formed. Through the detail analysis of these structures, we highlight the structural impact of these ligands on the structure, and their contribution to the MOFs properties and applications. Finally, we showcase the potential of bio-MOFs in several research areas such as CO2 capture, separation, catalysis, drug delivery and sensing.

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Section: Ligand Design In Mofsmentioning

confidence: 99%

Biologically derived metal organic frameworks

Anderson

Stylianou

2017

Coordination Chemistry Reviews

123

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“…Each ytterbium is connected to adjacent ytterbiums via either two or four carboxylato groups from the BDC linkers in a regular ) using the Cheetham-Rao-Feller nomenclature. 30 The topology of (1) is assigned as sra (the Al net in SrAl 2 , see ESI †), a commonly observed topology for materials with infinite rod-shaped secondary building units, 31 such as in the material MIL-53. 32 The structure of (1) is related to that of [Er 2 ĲBDC) 3 ĲDMF) 2 ] reported by Zhang et al 33 Both materials have the same local structure, connectivity and space group, with the difference being the presence of occluded water in (1).…”

Section: -19mentioning

confidence: 99%

Structural variety in ytterbium dicarboxylate frameworks and in situ study diffraction of their solvothermal crystallisation

et al. 2017

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aThe ytterbium 1,4-benzenedicarboxylate (BDC) framework [Yb 2 ĲBDC) 3 ĲDMF) 2 ]·H 2 O (1) crystallises from a N, N-dimethylformamide (DMF)-rich solution at 80-120°C. (1) is constructed from infinite chains of dicarboxylate-bridged seven-coordinate Yb atoms, cross-linked in two directions by BDC to yield diamond-shaped channels (sra topology) lined by coordinated DMF molecules and occluded water. Increasing the water content in the synthesis solution yields a material with more crystal water (2), in which the Yb centres are eight-coordinate and form dimers bridged by BDC to give two interpenetrating networks of pcu (α-Po) topology. Upon extended reaction in this water-rich solvent mixture, an alternative phase is formed: an anhydrous mixed BDC-formate, YbĲBDC)ĲHCO 2 ), (3), which has a pillared, layered structure, with formate produced by hydrolysis of the DMF. An isoreticular version of (2) can also be formed under similar conditions using 2,6-naphthalene-dicarboxylate (NDC) as linker: [Yb 2 ĲNDC) 3 ĲH 2 O) 4 ]·2DMF (4). Despite their different structures, (1) and (2) are calcined to a common porous, desolvated phase Yb 2 ĲBDC) 3 at 300°C. Using high energy X-rays at Diamond Light Source we are able to penetrate the solvothermal reaction vessels and to follow the formation of (1) and (2) in real time.This allows accurate crystallisation curves to be obtained from which qualitative kinetic information is extracted. Importantly, the high angular resolution of the in situ powder XRD patterns allows refinement of crystal structure: this permits the temporal evolution of unit cell parameters to be followed, which are ascribed to changes in coordinated solvent composition within the materials during their formation, while analysis of phase fraction allows kinetic parameters to be quantified using the nucleation-growth model of Gualtieri.

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“…MOFs can be readily functionalized using different organic building blocks thus imparting flexibility to tune the properties [8]. Metal-organic frameworks can also be tuned by using varied metals/metal clusters along with counter ions with different coordinating tendency [9][10][11][12][13]. MOFs have been classified as neutral and ionic MOFs (iMOFs) based on the framework charge [14].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Crystal Structure of a Zn(II)-Based MOF Bearing Neutral N-Donor Linker and SiF62− Anion

2018

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Abstract:A novel three-dimensional two-fold interpenetrated bi-porous metal-organic framework IPM-325 (IPM: IISER Pune Materials) having pcu topology was synthesized at room temperature. Single crystal X-ray diffraction (SC-XRD) study revealed that the compound crystallizes in monoclinic lattice with molecular formula {[Zn(L) 2 (SiF 6 )] (CH 2 Cl 2 ) xG} n where G = Guests). All metal centers were found to have octahedral geometry. From single crystal analysis it can be inferred that SiF 6 2− anion play a vital role in extending the dimensionality of the framework by bridging between two metal centers. Interestingly, IPM-325 exhibited two-step structural transformation maintaining the crystallinity of the framework as characterized by powder X-ray diffraction (PXRD).

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Structures of Metal–Organic Frameworks with Rod Secondary Building Units

Cited by 755 publications

References 281 publications

Biologically derived metal organic frameworks

Biologically derived metal organic frameworks

Structural variety in ytterbium dicarboxylate frameworks and in situ study diffraction of their solvothermal crystallisation

Synthesis and Crystal Structure of a Zn(II)-Based MOF Bearing Neutral N-Donor Linker and SiF62− Anion

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